Department of Chemistry, Jadavpur University, Kolkata 700 032, India.
Langmuir. 2011 Dec 20;27(24):15322-9. doi: 10.1021/la202094p. Epub 2011 Nov 15.
An ecofriendly solid catalyst has been synthesized by anchoring vanadium(IV) into organically modified MCM-41. First, the surface of Si-MCM-41 was modified with 3-aminopropyl-triethoxysilane (3-APTES), the amine group of which upon condensation with ortho-hydroxy-acetophenone affords a N(2)O(2)-type Schiff base moiety in the mesoporous matrix. The Schiff base moieties were used to anchor oxo-vanadium(IV) ions. The prepared catalyst has been characterized by UV-vis, IR spectroscopy, small-angle X-ray diffraction (SAX), nitrogen sorption, and transmission electron microscopy (TEM) studies. It is observed that the mesostructure has not been destroyed in the multistep synthesis procedure, as evidenced by SAX and TEM measurements. The catalyst has shown unprecedented high conversion as well as para selectivity toward the bromination of hydroxy aromatic compounds using aqueous 30% H(2)O(2)/KBr in water. The reaction proceeds according to the stoichiometric ratio, and the monobrominated product was obtained as the major product using a stoichiometric amount of the bromine source. The immobilized complex does not leach or decompose during the catalytic reactions, showing practical advantages over the free metal complex.
一种环保型固体催化剂已通过将钒(IV)锚定在有机修饰的 MCM-41 中合成。首先,用 3-氨丙基三乙氧基硅烷(3-APTES)修饰 Si-MCM-41,其胺基与邻羟基苯乙酮缩合在介孔基质中提供 N(2)O(2)-型希夫碱部分。希夫碱部分用于锚定氧代钒(IV)离子。通过紫外可见光谱、红外光谱、小角 X 射线衍射(SAX)、氮气吸附和透射电子显微镜(TEM)研究对制备的催化剂进行了表征。观察到介孔结构在多步合成过程中没有被破坏,这可以通过 SAX 和 TEM 测量来证明。该催化剂在水相中使用 30% H(2)O(2)/KBr 水溶液对羟基芳族化合物的溴化反应中表现出前所未有的高转化率和对映选择性。反应按照化学计量比进行,使用等摩尔量的溴源获得单溴化产物作为主要产物。固载化配合物在催化反应过程中不会浸出或分解,相对于游离金属配合物具有实际优势。